Temperature-dependent solid-state phase transition with twinning in the crystal structure of 4-meth­oxy­anilinium chloride

Uppu, R.M.; Babu, S.; Fronczek, F.R.

doi:10.1107/S2056989023010812

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ISSN: 2056-9890

Volume 80| Part 1| January 2024| Pages 58-61

https://doi.org/10.1107/S2056989023010812

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Temperature-dependent solid-state phase transition with twinning in the crystal structure of 4-methoxyanilinium chloride

Rao M. Uppu,^a ^* Sainath Babu ^a and Frank R. Fronczek ^b

^aDepartment of Environmental Toxicology, Southern University and A&M College, Baton Rouge, LA 70813, USA, and ^bDepartment of Chemistry, Louisiana State University, Baton Rouge, LA 70803, USA
^*Correspondence e-mail: rao_uppu@subr.edu

Edited by W. T. A. Harrison, University of Aberdeen, United Kingdom (Received 15 December 2023; accepted 17 December 2023; online 1 January 2024)

At room temperature, the title salt, C₇H₁₀NO⁺·Cl⁻, is orthorhombic, space group Pbca with Z′ = 1, as previously reported [Zhao (2009 ). Acta Cryst. E65, o2378]. Between 250 and 200 K, there is a solid-state phase transition to a twinned monoclinic P2₁/c structure with Z′ = 2. We report the high temperature structure at 250 K and the low-temperature structure at 100 K. In the low-temperature structure, the –NH₃ hydrogen atoms are ordered and this group has a different orientation in each independent molecule, in keeping with optimizing N—H⋯Cl hydrogen bonding, some of which are bifurcated: these hydrogen bonds have N⋯Cl distances in the range 3.1201 (8)–3.4047 (8) Å. In the single cation of the high-temperature structure, the NH hydrogen atoms are disordered into the average of the two low-temperature positions and the N⋯Cl hydrogen bond distances are in the range 3.1570 (15)–3.3323 (18) Å. At both temperatures, the methoxy group is nearly coplanar with the rest of the molecule, with the C—C—O—C torsion angles being −7.0 (2)° at 250 K and −6.94 (12) and −9.35 (12)° at 100 K. In the extended orthorhombic structure, (001) hydrogen-bonded sheets occur; in the monoclinic structure, the sheets propagate in the (010) plane.

Keywords: crystal structure; 4-alkoxyacetanilides; 4-alkoxyanilinium salts; nonsteroidal analgesics; mechanisms of toxicity.

CCDC references: 2314991; 2314990

1. Chemical context

4-Alkoxyacetanilides (4-AAs), represented by phenacetin, or N-(4-ethoxyphenyl)acetamide (C₁₀H₁₃NO₂), played a pivotal role in introducing synthetic fever reduction and non-opioid analgesics to the global pharmaceutical market in the early 1900s. The analgesic effects of 4-AAs result from their impact on the sensory tracts of the spinal cord, while their antipyretic actions predominantly occur in the brain, where they lower the temperature set point (Dalmann et al., 2015 ; Flower & Vane, 1972 ). In vivo, the primary metabolic pathway involves oxidative O-dealkylation, producing N-(4-hydroxyphenyl)acetamide, C₈H₉NO₃, a clinically significant analgesic (Nohmi et al., 1984 ). However, a minor fraction may undergo deacylation, leading to the formation of carcinogenic and kidney-damaging 4-alkoxyanilines Nohmi et al., 1984; Prescott, 1980 ). This study centers on the crystal structure analysis of the title salt, 4-methoxyaniline hydrochloride (4-methoxyanilinium chloride or 4-MAC), I, aiming to expound not only its potential kidney-damaging properties but also provide structural data for exploring molecular targets through molecular docking and molecular dynamic simulations.

2. Structural commentary

At room temperature (298 K), I crystallizes in the orthorhombic space group Pbca with one formula unit in the asymmetric unit. The cell dimensions are a = 8.8778 (5), b = 8.4660 (5), c = 21.7236 (11) Å and V = 1632.73 (16) Å³. Cooling the sample causes a solid-state phase transition to a twinned structure with lower symmetry and two formula units in the asymmetric unit. At 250 K, the structure is still orthorhombic, but at 200 K, the space group is monoclinic P2₁/c with a = 8.3772 (11), b = 21.715 (3), c = 8.8466 (12) Å, β = 90.039 (4)° and V = 1609.3 (4) Å³. At T = 100 K, the monoclinic cell parameters are a = 8.3039 (6), b = 21.6993 (15), c = 8.8495 (6) Å, β = 90.077 (2)° and V = 1594.58 (19) Å³.

The crystal structure at 250 K, shown in Fig. 1, closely aligns with the published structure (Zhao, 2009) except that we find disorder in the NH hydrogen atoms, while Zhao treated them as ordered. Using Zhao's intensity data, we do see evidence of a second orientation of the NH₃ group, and we also see it from our crystal when warmed to 298 K. The methoxy group in I is nearly coplanar with the rest of the molecule, with the torsion angle C7—O1—C4—C3 = −7.0 (2)°.

Figure 1
The asymmetric unit of the 250 K structure of I, with 50% displacement ellipsoids and hydrogen bonds indicated by blue dashed lines.

The asymmetric unit of the 100 K structure is shown in Fig. 2. The major difference between the two independent molecules is the conformation of the –NH₃ group, in which one molecule has one set of the disordered positions in the 250 K structure and the second has the other. As in the 250 K structure, the methoxy groups are twisted only slightly out of the planes of the aromatic rings, with C7—O1—C4—C3 and C14—O2—C11—C10 torsion angles of −6.94 (12) and −9.35 (12)°, respectively.

Figure 2
The asymmetric unit of the 100 K structure of I, with 50% displacement ellipsoids and hydrogen bonds indicated by blue dashed lines.

3. Supramolecular features

In both structures, the intermolecular interactions are predominantly N—H⋯Cl hydrogen bonds, as listed in Tables 1 and 2 and illustrated in Figs. 3 and 4. The N⋯Cl separations are in the range 3.1201 (8)–3.4047 (8) Å in the monoclinic 100 K structure and 3.1570 (15)–3.3323 (18) Å in the orthorhombic 250 K structure. In Fig. 4, it can be seen that for each NH₃ group, two of the H atoms are involved in direct hydrogen bonds and the third in a bifurcated N—H⋯(Cl,Cl) bond with two acceptors. The graph set (Etter et al., 1990 ) patterns are centrosymmetric R₄²(8) rings and R₂²(4) rings. At 250 K, (001) sheets arise in the extended structure and at 100 K similar sheets propagate in the (010) plane, due to the change in unit-cell settings.

Table 1
Hydrogen-bond geometry (Å, °) for I at 250 K

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯Cl1ⁱ	0.90	2.43	3.3265 (18)	174
N1—H2N⋯Cl1ⁱⁱ	0.90	2.40	3.1915 (15)	147
N1—H3N⋯CL1	0.90	2.45	3.1570 (16)	135
N1—H4N⋯Cl1ⁱⁱⁱ	0.90	2.43	3.3323 (18)	180
N1—H5N⋯Cl1	0.90	2.36	3.1570 (15)	148
N1—H6N⋯Cl1ⁱⁱ	0.90	2.49	3.1915 (17)	136
C6—H6⋯Cl1ⁱ	0.94	2.82	3.6323 (16)	145
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, z]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (iii) .

Table 2
Hydrogen-bond geometry (Å, °) for I at 100 K

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H11N⋯Cl2	0.880 (15)	2.279 (15)	3.1450 (8)	167.7 (13)
N1—H12N⋯Cl1ⁱ	0.870 (14)	2.573 (14)	3.2480 (7)	135.2 (13)
N1—H12N⋯Cl2ⁱⁱ	0.870 (14)	2.735 (15)	3.3797 (8)	132.1 (12)
N1—H13N⋯Cl1	0.926 (15)	2.304 (16)	3.2080 (8)	165.0 (13)
N2—H21N⋯Cl1ⁱⁱⁱ	0.901 (14)	2.487 (15)	3.2318 (8)	140.3 (12)
N2—H21N⋯Cl2^iv	0.901 (14)	2.795 (14)	3.4047 (8)	126.2 (11)
N2—H22N⋯Cl1	0.899 (14)	2.300 (15)	3.1916 (8)	171.3 (12)
N2—H23N⋯Cl2	0.907 (15)	2.234 (15)	3.1201 (8)	165.5 (13)
C2—H2⋯Cl1	0.95	2.98	3.7487 (8)	139
C6—H6⋯Cl2ⁱⁱ	0.95	2.77	3.6055 (8)	147
Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .

Figure 3
Hydrogen bonding in the 250 K structure of I.

Figure 4
Hydrogen bonding in the 100 K structure of I.

4. Database survey

A review of the literature revealed that the room temperature (298 K) structure of 4-methoxyanilinium chloride was previously reported (Zhao, 2009; Cambridge Structural Database refcode CUCTUQ). Similarly, the structure of 4-ethoxyanilinium chloride at 100 K has been documented (Fu, 2010 ; Hines et al., 2023 ). However, these studies did not provide information on phase transitions and twinning.

5. Synthesis and crystallization

A saturated solution of the title compound, C₇H₁₀ClNO (CAS 20265-97-8 from AmBeed, Arlington Heights, IL, USA) in boiling water was allowed to pass through a short column of activated charcoal. The resulting colorless solution (eluent) was left to cool to room temperature and evaporate slowly in the dark. Pink laths of I, prepared through this process, were suitable for X-ray diffraction studies.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. For the structure at 250 K, all the H atoms were located in difference maps and those on carbon were relocated to geometrically idealized positions with C—H = 0.94 Å and U_iso(H) = 1.2U_eq(C) for the aromatic C atoms and C—H = 0.97 Å and U_iso(H) = 1.5U_eq(C) for the methyl group. The N-bound H atoms were idealized as six half-populated sites at 60° torsional intervals with N—H = 0.90 Å and U_iso(H) = 1.5U_eq(N) and the torsion angle was refined. For the structure at 100 K, the H atoms were handled similarly, except that C—H distances were fixed at 0.95 Å for aromatic C atoms and 0.98 Å for the methyl group, and the H atoms on N were ordered with their positions individually refined. The twin law for the monoclinic structure is (1 0 0, 0 −1 0, 0 0 −1) and the BASF parameter refined to 0.4484 (6).

Table 3
Experimental details

	I at 250 K	I at 100 K
Crystal data
Chemical formula	C₇H₁₀NO⁺·Cl⁻	C₇H₁₀NO⁺·Cl⁻
M_r	159.61	159.61
Crystal system, space group	Orthorhombic, Pbca	Monoclinic, P2₁/c
Temperature (K)	250	100
a, b, c (Å)	8.8689 (4), 8.4361 (3), 21.7319 (9)	8.3039 (6), 21.6993 (15), 8.8495 (6)
α, β, γ (°)	90, 90, 90	90, 90.077 (2), 90
V (Å³)	1625.96 (12)	1594.58 (19)
Z	8	8
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	0.40	0.41
Crystal size (mm)	0.34 × 0.31 × 0.15	0.43 × 0.41 × 0.21

Data collection
Diffractometer	Bruker Kappa APEXII CCD	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )	Multi-scan (SADABS; Krause et al., 2015)
T_min, T_max	0.896, 0.942	0.873, 0.919
No. of measured, independent and observed [I > 2σ(I)] reflections	73425, 2717, 2019	48397, 10832, 9310
R_int	0.050	0.033
(sin θ/λ)_max (Å⁻¹)	0.737	0.940

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.102, 1.08	0.033, 0.075, 1.06
No. of reflections	2717	10832
No. of parameters	93	202
H-atom treatment	H-atom parameters constrained	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.22	0.47, −0.28
Computer programs: APEX3 and SAINT (Bruker, 2016 ), SHELXT2018/2 (Sheldrick, 2015 ), SHELXL2018/1 (Sheldrick, 2015), Mercury (Macrae et al., 2020 ), and publCIF (Westrip, 2010 ).

Supporting information

CCDC references: 2314991; 2314990

Crystal structure: contains datablocks I_250K, I_100K, global. DOI: https://doi.org/10.1107/S2056989023010812/hb8089sup1.cif

Structure factors: contains datablock I_250K. DOI: https://doi.org/10.1107/S2056989023010812/hb8089I_250Ksup2.hkl

Structure factors: contains datablock I_100K. DOI: https://doi.org/10.1107/S2056989023010812/hb8089I_100Ksup3.hkl

checkCIF report

Computing details top

4-Methoxyanilinium chloride (I_250K) top

Crystal data top

C₇H₁₀NO⁺·Cl⁻	D_x = 1.304 Mg m⁻³
M_r = 159.61	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 9997 reflections
a = 8.8689 (4) Å	θ = 3.8–27.4°
b = 8.4361 (3) Å	µ = 0.40 mm⁻¹
c = 21.7319 (9) Å	T = 250 K
V = 1625.96 (12) Å³	Lath fragment, pink
Z = 8	0.34 × 0.31 × 0.15 mm
F(000) = 672

Data collection top

Bruker Kappa APEXII CCD diffractometer	2717 independent reflections
Radiation source: fine-focus sealed tube	2019 reflections with I > 2σ(I)
TRIUMPH curved graphite monochromator	R_int = 0.050
φ and ω scans	θ_max = 31.6°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −13→13
T_min = 0.896, T_max = 0.942	k = −12→12
73425 measured reflections	l = −32→32

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.041	w = 1/[σ²(F_o²) + (0.0348P)² + 0.6343P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.102	(Δ/σ)_max = 0.001
S = 1.08	Δρ_max = 0.24 e Å⁻³
2717 reflections	Δρ_min = −0.21 e Å⁻³
93 parameters	Extinction correction: SHELXL-2017/1 (Sheldrick 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0070 (9)

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cl1	0.74847 (4)	0.51434 (4)	0.52125 (2)	0.03992 (12)
O1	0.65326 (14)	0.80202 (15)	0.20491 (5)	0.0514 (3)
N1	0.52441 (19)	0.75043 (18)	0.45535 (6)	0.0547 (4)
H1N	0.584233	0.818422	0.475901	0.082*	0.5
H2N	0.427238	0.776832	0.461481	0.082*	0.5
H3N	0.540574	0.651270	0.469129	0.082*	0.5
H4N	0.450464	0.679260	0.461773	0.082*	0.5
H5N	0.607459	0.720851	0.476193	0.082*	0.5
H6N	0.494123	0.846412	0.468545	0.082*	0.5
C1	0.55894 (17)	0.75820 (17)	0.38936 (7)	0.0388 (3)
C2	0.48090 (17)	0.66401 (19)	0.34891 (7)	0.0427 (3)
H2	0.408003	0.592462	0.363560	0.051*
C3	0.51002 (17)	0.67476 (19)	0.28628 (7)	0.0406 (3)
H3	0.456473	0.610978	0.258349	0.049*
C4	0.61767 (17)	0.77925 (17)	0.26521 (6)	0.0371 (3)
C5	0.6976 (2)	0.8710 (2)	0.30673 (8)	0.0481 (4)
H5	0.772702	0.940379	0.292416	0.058*
C6	0.6681 (2)	0.8615 (2)	0.36875 (7)	0.0484 (4)
H6	0.721776	0.924909	0.396768	0.058*
C7	0.5863 (2)	0.6992 (3)	0.16061 (8)	0.0638 (5)
H7A	0.611485	0.590164	0.170382	0.096*
H7B	0.624205	0.725123	0.119973	0.096*
H7C	0.477664	0.712315	0.161343	0.096*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.03990 (18)	0.04090 (19)	0.03894 (18)	−0.00135 (14)	−0.00086 (16)	0.00395 (13)
O1	0.0576 (7)	0.0614 (7)	0.0351 (6)	0.0028 (6)	0.0091 (5)	0.0037 (5)
N1	0.0653 (9)	0.0622 (9)	0.0364 (7)	0.0194 (7)	0.0085 (6)	0.0064 (6)
C1	0.0407 (7)	0.0429 (7)	0.0328 (6)	0.0138 (6)	0.0038 (6)	0.0053 (6)
C2	0.0373 (7)	0.0436 (8)	0.0473 (8)	−0.0006 (6)	0.0065 (6)	0.0055 (6)
C3	0.0375 (8)	0.0435 (8)	0.0407 (7)	0.0009 (6)	0.0001 (6)	−0.0035 (6)
C4	0.0375 (7)	0.0391 (7)	0.0347 (7)	0.0073 (6)	0.0040 (6)	0.0036 (5)
C5	0.0484 (9)	0.0496 (9)	0.0463 (9)	−0.0129 (7)	0.0036 (7)	0.0052 (7)
C6	0.0528 (9)	0.0504 (9)	0.0419 (8)	−0.0056 (7)	−0.0049 (7)	−0.0028 (7)
C7	0.0643 (12)	0.0896 (14)	0.0374 (8)	0.0102 (11)	0.0031 (8)	−0.0106 (9)

Geometric parameters (Å, º) top

O1—C4	1.3615 (17)	C2—C3	1.388 (2)
O1—C7	1.425 (2)	C2—H2	0.9400
N1—C1	1.4679 (19)	C3—C4	1.378 (2)
N1—H1N	0.9000	C3—H3	0.9400
N1—H2N	0.9000	C4—C5	1.384 (2)
N1—H3N	0.9000	C5—C6	1.375 (2)
N1—H4N	0.9000	C5—H5	0.9400
N1—H5N	0.9000	C6—H6	0.9400
N1—H6N	0.9000	C7—H7A	0.9700
C1—C2	1.372 (2)	C7—H7B	0.9700
C1—C6	1.377 (2)	C7—H7C	0.9700

C4—O1—C7	117.88 (14)	C4—C3—C2	119.77 (14)
C1—N1—H1N	109.5	C4—C3—H3	120.1
C1—N1—H2N	109.5	C2—C3—H3	120.1
H1N—N1—H2N	109.5	O1—C4—C3	124.81 (14)
C1—N1—H3N	109.5	O1—C4—C5	115.46 (14)
H1N—N1—H3N	109.5	C3—C4—C5	119.73 (13)
H2N—N1—H3N	109.5	C6—C5—C4	120.60 (15)
C1—N1—H4N	109.5	C6—C5—H5	119.7
C1—N1—H5N	109.5	C4—C5—H5	119.7
H4N—N1—H5N	109.5	C5—C6—C1	119.28 (15)
C1—N1—H6N	109.5	C5—C6—H6	120.4
H4N—N1—H6N	109.5	C1—C6—H6	120.4
H5N—N1—H6N	109.5	O1—C7—H7A	109.5
C2—C1—C6	120.83 (14)	O1—C7—H7B	109.5
C2—C1—N1	119.65 (14)	H7A—C7—H7B	109.5
C6—C1—N1	119.51 (15)	O1—C7—H7C	109.5
C1—C2—C3	119.76 (14)	H7A—C7—H7C	109.5
C1—C2—H2	120.1	H7B—C7—H7C	109.5
C3—C2—H2	120.1

C6—C1—C2—C3	−1.2 (2)	C2—C3—C4—C5	1.0 (2)
N1—C1—C2—C3	177.97 (14)	O1—C4—C5—C6	178.05 (15)
C1—C2—C3—C4	0.4 (2)	C3—C4—C5—C6	−1.5 (2)
C7—O1—C4—C3	−7.0 (2)	C4—C5—C6—C1	0.7 (3)
C7—O1—C4—C5	173.48 (15)	C2—C1—C6—C5	0.7 (2)
C2—C3—C4—O1	−178.58 (14)	N1—C1—C6—C5	−178.52 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···Cl1ⁱ	0.90	2.43	3.3265 (18)	174
N1—H2N···Cl1ⁱⁱ	0.90	2.40	3.1915 (15)	147
N1—H3N···CL1	0.90	2.45	3.1570 (16)	135
N1—H4N···Cl1ⁱⁱⁱ	0.90	2.43	3.3323 (18)	180
N1—H5N···Cl1	0.90	2.36	3.1570 (15)	148
N1—H6N···Cl1ⁱⁱ	0.90	2.49	3.1915 (17)	136
C6—H6···Cl1ⁱ	0.94	2.82	3.6323 (16)	145

Symmetry codes: (i) −x+3/2, y+1/2, z; (ii) x−1/2, −y+3/2, −z+1; (iii) −x+1, −y+1, −z+1.

4-Methoxyanilinium chloride (I_100K) top

Crystal data top

C₇H₁₀NO⁺·Cl⁻	F(000) = 672
M_r = 159.61	D_x = 1.330 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.3039 (6) Å	Cell parameters from 9875 reflections
b = 21.6993 (15) Å	θ = 3.4–41.5°
c = 8.8495 (6) Å	µ = 0.41 mm⁻¹
β = 90.077 (2)°	T = 100 K
V = 1594.58 (19) Å³	Needle fragment, pink
Z = 8	0.43 × 0.41 × 0.21 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	10832 independent reflections
Radiation source: fine-focus sealed tube	9310 reflections with I > 2σ(I)
TRIUMPH curved graphite monochromator	R_int = 0.033
φ and ω scans	θ_max = 41.9°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −15→15
T_min = 0.873, T_max = 0.919	k = −40→40
48397 measured reflections	l = −16→15

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.033	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.075	w = 1/[σ²(F_o²) + (0.0336P)² + 0.1702P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
10832 reflections	Δρ_max = 0.47 e Å⁻³
202 parameters	Δρ_min = −0.28 e Å⁻³
0 restraints

Special details top

Refinement. Refined as a 2-component twin

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.46961 (2)	0.52412 (2)	0.74414 (2)	0.01433 (3)
Cl2	1.00704 (2)	0.51981 (2)	0.75416 (2)	0.01431 (3)
O1	0.81503 (9)	0.79863 (3)	0.36295 (8)	0.01972 (12)
N1	0.75005 (10)	0.54837 (3)	0.50236 (8)	0.01524 (11)
H11N	0.8313 (18)	0.5382 (6)	0.5613 (16)	0.023*
H12N	0.7496 (18)	0.5254 (6)	0.4219 (16)	0.023*
H13N	0.6580 (18)	0.5390 (6)	0.5566 (17)	0.023*
C1	0.75955 (9)	0.61391 (3)	0.46333 (8)	0.01282 (11)
C2	0.66656 (10)	0.65590 (4)	0.54219 (9)	0.01463 (13)
H2	0.592916	0.642048	0.616899	0.018*
C3	0.68159 (10)	0.71877 (4)	0.51130 (9)	0.01510 (12)
H3	0.618985	0.747903	0.565734	0.018*
C4	0.78835 (10)	0.73857 (3)	0.40075 (9)	0.01439 (12)
C5	0.87901 (11)	0.69542 (4)	0.31922 (10)	0.01746 (14)
H5	0.949889	0.708935	0.241833	0.021*
C6	0.86556 (10)	0.63310 (4)	0.35115 (10)	0.01644 (13)
H6	0.928009	0.603820	0.297051	0.020*
C7	0.71299 (15)	0.84409 (4)	0.43121 (12)	0.02472 (19)
H7A	0.600193	0.834617	0.408214	0.037*
H7B	0.739987	0.884893	0.391123	0.037*
H7C	0.729058	0.843809	0.540940	0.037*
O2	0.69262 (8)	0.20673 (3)	0.82982 (8)	0.01905 (11)
N2	0.73702 (9)	0.45944 (3)	0.94929 (8)	0.01440 (11)
H21N	0.7316 (18)	0.4677 (6)	1.0489 (16)	0.022*
H22N	0.6576 (18)	0.4795 (6)	0.9008 (16)	0.022*
H23N	0.8253 (18)	0.4776 (6)	0.9085 (16)	0.022*
C8	0.72962 (9)	0.39304 (3)	0.91915 (8)	0.01249 (11)
C9	0.82458 (10)	0.35313 (4)	1.00292 (9)	0.01498 (12)
H9	0.895113	0.368738	1.078368	0.018*
C10	0.81599 (10)	0.28992 (3)	0.97583 (9)	0.01480 (12)
H10	0.880248	0.262235	1.033186	0.018*
C11	0.71267 (9)	0.26745 (3)	0.86417 (9)	0.01383 (12)
C12	0.61959 (10)	0.30835 (4)	0.77920 (10)	0.01777 (14)
H12	0.550715	0.293062	0.702026	0.021*
C13	0.62716 (10)	0.37124 (4)	0.80690 (10)	0.01671 (13)
H13	0.563053	0.399067	0.749807	0.020*
C14	0.80131 (12)	0.16348 (4)	0.89757 (11)	0.02172 (16)
H14A	0.912339	0.174734	0.872250	0.033*
H14B	0.778211	0.122036	0.859247	0.033*
H14C	0.787721	0.164090	1.007547	0.033*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.01254 (6)	0.01532 (6)	0.01511 (7)	−0.00041 (5)	−0.00015 (8)	0.00016 (6)
Cl2	0.01256 (6)	0.01453 (6)	0.01584 (7)	−0.00127 (5)	−0.00072 (8)	−0.00022 (6)
O1	0.0248 (3)	0.0133 (2)	0.0211 (3)	−0.0012 (2)	−0.0017 (2)	0.0031 (2)
N1	0.0200 (3)	0.0126 (2)	0.0132 (3)	−0.0018 (2)	−0.0019 (2)	0.00002 (19)
C1	0.0144 (3)	0.0126 (2)	0.0114 (3)	−0.0006 (2)	−0.0012 (2)	−0.0003 (2)
C2	0.0154 (3)	0.0155 (3)	0.0130 (3)	−0.0001 (2)	0.0007 (2)	−0.0002 (2)
C3	0.0168 (3)	0.0149 (3)	0.0136 (3)	0.0019 (2)	−0.0001 (2)	−0.0010 (2)
C4	0.0158 (3)	0.0133 (3)	0.0140 (3)	−0.0011 (2)	−0.0034 (2)	0.0009 (2)
C5	0.0187 (3)	0.0169 (3)	0.0168 (3)	−0.0015 (3)	0.0047 (3)	0.0013 (3)
C6	0.0182 (3)	0.0150 (3)	0.0161 (3)	0.0007 (2)	0.0037 (3)	−0.0010 (2)
C7	0.0372 (6)	0.0143 (3)	0.0226 (4)	0.0052 (3)	−0.0034 (4)	0.0003 (3)
O2	0.0220 (3)	0.0129 (2)	0.0222 (3)	−0.0016 (2)	−0.0008 (2)	−0.0029 (2)
N2	0.0182 (3)	0.0126 (2)	0.0124 (3)	−0.0008 (2)	0.0008 (2)	0.00002 (19)
C8	0.0136 (3)	0.0124 (2)	0.0115 (3)	−0.0012 (2)	0.0008 (2)	−0.0003 (2)
C9	0.0166 (3)	0.0149 (3)	0.0134 (3)	−0.0003 (2)	−0.0026 (3)	−0.0014 (2)
C10	0.0169 (3)	0.0139 (3)	0.0136 (3)	0.0007 (2)	−0.0013 (2)	−0.0006 (2)
C11	0.0147 (3)	0.0129 (3)	0.0139 (3)	−0.0023 (2)	0.0023 (2)	−0.0014 (2)
C12	0.0193 (3)	0.0160 (3)	0.0180 (4)	−0.0021 (2)	−0.0055 (3)	−0.0018 (2)
C13	0.0181 (3)	0.0153 (3)	0.0167 (3)	−0.0010 (2)	−0.0050 (3)	0.0011 (2)
C14	0.0280 (4)	0.0136 (3)	0.0236 (4)	0.0022 (3)	0.0032 (3)	−0.0011 (3)

Geometric parameters (Å, º) top

O1—C4	1.3636 (10)	O2—C11	1.3624 (9)
O1—C7	1.4343 (12)	O2—C14	1.4330 (11)
N1—C1	1.4655 (10)	N2—C8	1.4667 (10)
N1—H11N	0.880 (15)	N2—H21N	0.901 (14)
N1—H12N	0.870 (14)	N2—H22N	0.899 (14)
N1—H13N	0.926 (15)	N2—H23N	0.907 (15)
C1—C2	1.3838 (11)	C8—C9	1.3856 (11)
C1—C6	1.3915 (11)	C8—C13	1.3900 (11)
C2—C3	1.3971 (11)	C9—C10	1.3941 (11)
C2—H2	0.9500	C9—H9	0.9500
C3—C4	1.3893 (12)	C10—C11	1.3957 (11)
C3—H3	0.9500	C10—H10	0.9500
C4—C5	1.4020 (12)	C11—C12	1.3961 (11)
C5—C6	1.3860 (11)	C12—C13	1.3879 (11)
C5—H5	0.9500	C12—H12	0.9500
C6—H6	0.9500	C13—H13	0.9500
C7—H7A	0.9800	C14—H14A	0.9800
C7—H7B	0.9800	C14—H14B	0.9800
C7—H7C	0.9800	C14—H14C	0.9800

C4—O1—C7	117.24 (7)	C11—O2—C14	117.60 (7)
C1—N1—H11N	109.9 (9)	C8—N2—H21N	111.7 (8)
C1—N1—H12N	111.4 (9)	C8—N2—H22N	111.0 (8)
H11N—N1—H12N	110.1 (13)	H21N—N2—H22N	109.5 (12)
C1—N1—H13N	112.4 (8)	C8—N2—H23N	112.8 (8)
H11N—N1—H13N	105.7 (12)	H21N—N2—H23N	110.2 (13)
H12N—N1—H13N	107.2 (13)	H22N—N2—H23N	101.1 (12)
C2—C1—C6	121.11 (7)	C9—C8—C13	121.13 (7)
C2—C1—N1	119.33 (7)	C9—C8—N2	119.54 (7)
C6—C1—N1	119.53 (7)	C13—C8—N2	119.32 (7)
C1—C2—C3	119.63 (8)	C8—C9—C10	119.60 (7)
C1—C2—H2	120.2	C8—C9—H9	120.2
C3—C2—H2	120.2	C10—C9—H9	120.2
C4—C3—C2	119.81 (7)	C9—C10—C11	119.78 (7)
C4—C3—H3	120.1	C9—C10—H10	120.1
C2—C3—H3	120.1	C11—C10—H10	120.1
O1—C4—C3	124.91 (7)	O2—C11—C10	124.79 (7)
O1—C4—C5	115.12 (7)	O2—C11—C12	115.29 (7)
C3—C4—C5	119.96 (7)	C10—C11—C12	119.91 (7)
C6—C5—C4	120.22 (8)	C13—C12—C11	120.33 (7)
C6—C5—H5	119.9	C13—C12—H12	119.8
C4—C5—H5	119.9	C11—C12—H12	119.8
C5—C6—C1	119.26 (7)	C12—C13—C8	119.23 (7)
C5—C6—H6	120.4	C12—C13—H13	120.4
C1—C6—H6	120.4	C8—C13—H13	120.4
O1—C7—H7A	109.5	O2—C14—H14A	109.5
O1—C7—H7B	109.5	O2—C14—H14B	109.5
H7A—C7—H7B	109.5	H14A—C14—H14B	109.5
O1—C7—H7C	109.5	O2—C14—H14C	109.5
H7A—C7—H7C	109.5	H14A—C14—H14C	109.5
H7B—C7—H7C	109.5	H14B—C14—H14C	109.5

C6—C1—C2—C3	−1.43 (12)	C13—C8—C9—C10	−0.84 (12)
N1—C1—C2—C3	176.47 (7)	N2—C8—C9—C10	179.11 (7)
C1—C2—C3—C4	0.67 (12)	C8—C9—C10—C11	0.36 (12)
C7—O1—C4—C3	−6.94 (12)	C14—O2—C11—C10	−9.35 (12)
C7—O1—C4—C5	173.41 (8)	C14—O2—C11—C12	171.16 (8)
C2—C3—C4—O1	−178.79 (8)	C9—C10—C11—O2	−178.87 (8)
C2—C3—C4—C5	0.84 (12)	C9—C10—C11—C12	0.60 (12)
O1—C4—C5—C6	178.02 (8)	O2—C11—C12—C13	178.42 (8)
C3—C4—C5—C6	−1.65 (12)	C10—C11—C12—C13	−1.10 (13)
C4—C5—C6—C1	0.91 (13)	C11—C12—C13—C8	0.63 (13)
C2—C1—C6—C5	0.63 (12)	C9—C8—C13—C12	0.35 (13)
N1—C1—C6—C5	−177.26 (8)	N2—C8—C13—C12	−179.60 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11N···Cl2	0.880 (15)	2.279 (15)	3.1450 (8)	167.7 (13)
N1—H12N···Cl1ⁱ	0.870 (14)	2.573 (14)	3.2480 (7)	135.2 (13)
N1—H12N···Cl2ⁱⁱ	0.870 (14)	2.735 (15)	3.3797 (8)	132.1 (12)
N1—H13N···Cl1	0.926 (15)	2.304 (16)	3.2080 (8)	165.0 (13)
N2—H21N···Cl1ⁱⁱⁱ	0.901 (14)	2.487 (15)	3.2318 (8)	140.3 (12)
N2—H21N···Cl2^iv	0.901 (14)	2.795 (14)	3.4047 (8)	126.2 (11)
N2—H22N···Cl1	0.899 (14)	2.300 (15)	3.1916 (8)	171.3 (12)
N2—H23N···Cl2	0.907 (15)	2.234 (15)	3.1201 (8)	165.5 (13)
C2—H2···Cl1	0.95	2.98	3.7487 (8)	139
C6—H6···Cl2ⁱⁱ	0.95	2.77	3.6055 (8)	147

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y+1, −z+1; (iii) −x+1, −y+1, −z+2; (iv) −x+2, −y+1, −z+2.

Funding information

Research reported in this publication was supported by an Institutional Development Award (IDeA) from the National Institute of General Medical Sciences of the National Institutes of Health under grant number P2O GM103424–21. The upgrade of the diffractometer was made possible by grant No. LEQSF (2011–12)-ENH-TR-01, administered by the Louisiana Board of Regents. Its contents are solely the responsibility of authors and do not represent the official views of NIH, NIGMS, or US DoE.

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Volume 80| Part 1| January 2024| Pages 58-61

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Temperature-dependent solid-state phase transition with twinning in the crystal structure of 4-meth­­oxy­anilinium chloride

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

6. Refinement

Supporting information

Funding information

References

research communications

Temperature-dependent solid-state phase transition with twinning in the crystal structure of 4-methoxyanilinium chloride

3. Supramolecular features